Preparation of nitrogen-containing materials from olefins



July 28, 1953 H. D. HARTOUGH ErAL 2,647,117

PREPARATION OF NITROGEN-CONTAINING MATERIALS FROM OLEFINS Filed Nov. 29, 1949 3 Sheets-Sheet l g firm/mfr July 28, 1953 H. D. HARTOUGH ET Al. 2,647,117

PREPARATION 0F NITROGEN-CONTAIN'ING MATERIALS FROM OLEFINS Filed NOV. 29, 1949 3 Sheets-Sheet 2 July 28, 1953 H. D. HARToUGH ET AL 2,647,117

PREPARATION OF NITROGEN-CONTAINING MATERIALS FROM OLEFINS Filed Nov. 29, 1949 5 Sheets-Sheet 3 R Ru WHEN Y OH R Rl Ril RQ c 2 CH2 O N Hz 0H H20 OIH 0H I R -0-cH2 N Hx P -0-cH2 N Rl c b c R., I- Na 0H w. I I Rl" C CH2 ROC' cHQ XXII XXII a INVENTORS #0M/R012 Hmmm# BY fnsfPf//f/rf/ Pg J/.

55mm/A L. nsf/ l F when R or R is hydrogen and R and R'" are 1,3-oxazines are produced is readily recognized hydrogen, the other substituent shall be a Subupon inspection of the following equations: stituent having a double bond in conjugation with Knorrs classical reaction:

the double bond in theuparent olenh Similarly, AGH CH OH u CH CH having a double bond in conjugation with thev \CHz-oH-0H 160 C' CH2-o 2 double bond of the parent olen. Thus, for exL-J ample, styrene participateszin this reactionv-hav j gj; ing a composition corresponding to i when R is hydrogen, R is A'R.; isyhydro--- v gen and R" is hydrogen. A9,*1l-1inoleic acid. is

also included since it has -a; composition" corre# 557 l ospondng t0 -OH -CHaN=CH(HX) ;M/ s R, R,1L J When R and R are-hydrogen, R' is i l y A,

- l I substituted tet h d -1,3 G '-n d aik 1-f CHHZMCH CH 25 oxuzmehydhurje allliluie'riyrohliqm and R 1S (CHCQOH 91' I -Inthe presence of excess formaldehyde, II is I n I Y H n converted to N-methyloltetrahydro 1,3 oxazine I\C`=' C`/ which in turn is converted by more formaldehyde f to N-methyltetrahydro-1,3-oxazine and the bis- QH3 CH2 4CH=Q 'YKJHDYCQOE v 30 i(tetrahydro-LB-oxazino) methane. v l Eleostearlc acid,--A9,11,1-3o'ctadecatr1enoic acid, 1n addition to the foregoing aminesnl diox and similar carboxylic acidshaving two or more anes 0f the general Structure A conjugated double bonds participate in this reaction. Examples of otherv carboxylic acids which fr L R\ can participate in this novelireaction are meth- 3" v C- acrylic acid,l isocrotonic acid and ,the like. In 1- d v R/ `other Words, `vvhen neitherof the substituents v t R', 00H10 attached to a single double bodcarbon 'atom vv v H2 is hydrogen, it is' not necessary that'a double-f0 l- .y

bond be inconjugation with the 'double bond' of Rm the parent olefin. Thus, acrylicaidis not in'- n eluded in thegroup of operative carboxylicacids are also formed as OY-products m some 111 because three of the. substituent .are hydrogen stances 1n trace amounts but generally to the und the fourth substituent dues 'not have 'ain' oief f @It 0f, about 5 Per Gent 0f. the total Productsnic vorummm@double boudin conjugation with 45 'I 'tls to be noted that Kohn reported'm Montt' the double bond of the'parentolei'in-asis mani- Shaft?" 25' 827! 833 851 (1904) the prepatnatlon fest uponins'pection of the str ucturl'formula @ith-e '4A-6'trlmethyl'tetmhydr13'9XaZme'ais of acrylic acid. i A Y -f Va result of the reaction between-1,1-d1methyl-1- amlno-S-hydroxybutane and aqueous formalde- H\' /E 50 hyde." This reaction can be represente'dby the /C=G\CH) -f -Y equation: y H` CQOHU l /CH 387 CHO Another group of compounds Whichparticipate 'cHioHlfoHa-c in this reaction are the rvinyl `su'lfo'rilels,"vinyl .1 E i Ilm, OHV ethersvinylthioethers and vinylhalid'e's'."` j. A H, In general, the products are 'substitute'dtetral j H n CHI' hydro-1,3-oxazines. The'products oan'be'rnono-iL y /5\l 'A di, tr, or tetra-substituted since one or both 'CH3-W I3-QH H10 of the hydrogens attached to the carbonvatoms 'j' o1l BNR of the oxazine ringderived from"the'ol'enic re- 50 I actant may be'substituted by'alkyl', aryl, alkaryl l varalkyl,'cycloalkyl or heterocyclic' substituents' a's 1 emphasized hereinbeiore.v Manife'stly Kohns reaction is different frorn'the It is to be noted' that the ox'azinesl'were'first "postulated mechanism of the present method-in recognizedabout 5G years ago whenKnorr' ob- 6'5 that it linvolves solely a ring closure of a hy tained tetrahydro'-1,4`oxazine heating didroXy'lated alkyl amine Whereas the present ethanolamine 'with hydrochloric' acid at 160 C. vmethod involves an olenic compound, formalde- 'Morphoiine the common name'for' tetrahydrohyde and ammonium hydrohalide ora primary 1,4 0Xazne can 3150.13@ made by 1the-action'of amine hydrohalide. Itl will also be noted that sulfuric acid on triethanolamine. (Morton, The 70 lKohns tetrahydro-LB-oxazines are substituted Chemistry of Heterocyclic Compounds? (1946), at the 4 and 6 positions whereas theproduct's 47,7.) The difference between'thefclassicalre- 0f the present methOd 0f prepalatfm are Subaction tol producemorpholine; tetrahyd'ro-lgfi- 'Stituted'at'the 4, '5 0r6 positions of the tetraoxazine, and the'postulated reaction of the preshydrooxazine ring. i f

ent invention whereby `Srulustimt-ed; 'tetrahydr'o- 75 In general, it has `been found that olei'nica.,k

@sammy compounds having a composition corresponding (where Y is the alkyl, cycloalkyl or aryl group of to the forfnula ythe-primarylamine hydrohalide).

R R" l thespecial case when Y=CH3 Compound IV R/ \R, 5 Thevfirst step illustrated in Fig. III can be am- Wheren R, R, R and R'" have the signianee plmed by the eqatm-n given "hereinbefore react with a hydrhale of (3) ammo'iiabr a primary airline or a priinary damine to produce formaldimines,4 tetrahydrof 3 'we fri-'o2- XXII When Compound IV (Fig. I), XII (Fig. II), XIIb (Fig. IIa) or XXII (Fig. III) is treated with strong caustic such a's sodiunfi or potassium hydroxide, the free amines, IVa, XIIa. IVa and yXX-Ha, re's'peabit/ely are 4set free as indicated in the following A4equation:

i o-OHRNLHX) .I =l NOH Gamma-hydroxyalkylform substituted tetrahydro-1,3

aldimine hydrohalide A oxazine hydrohalide IV LV-R l, v Y l Similarly, the rst yslerillustrated in Fig. 1I 45 can be amplified by the equation where Y is an /C- -0GH2N +NaX I alle@ .erwachen-gg n0g-rege than .18 @man Xn Rf tal atoms; an'varyigrou-p-orla cycloalkyl'fgmup. ,xm R" -XXII Rf" v A A Ww-, IVa 56013120 .--SNii-,Ym X11 IV 55 XX-Ha When Compound II, the tetrahydro-l-xaiine R\ hydrohalideyv is treated with afurther amount of formaldehyde and' Whn'a'rnaterialezcess 'f the .OH Y R/ inolalljpropo'rtio'n of-formaldehyde setforthliefre- V i. *l inbefore ispreent in the original reaction mix- CH2N(HX) RQ ture, the N/-methylol-tetrahydro-1,3-oxazine hyy 1 drohalide (III' is formed as represented bythe CH: R reaction \C -CHz-lurrx) (5) Rl Y R\ C- H Rn 0H -1- l \C 70 R' -OCH2N(HX') CH o R,l/l R" om XI xii N-methylol-tetrahydro-1,3-oxazine hydrohalide N-methyl-tetrahydro 1,3 oxazine hydrohalide (Compound IV) is formed in accordance with Equation 6 when (1) Compound III is treated with a further amount of formaldehyde in the molal ratio of 1:1 and (2) (when using ammonium halide) the excess of formaldehyde in the original reaction mixture is suicient.

N-methyl-tetrahydro 1,3-oxazine hydrohalide When conditions are conducive, a molecule of Compound IIa condenses With a molecule of Compound Illa to form Compound V, bis- (tetrahydro-1,3-oxazino)-methane The same end is attained when compound IIa and formaldehyde are reacted in the molal proportion of 2:1 in ac- RHI Va I I However, the corresponding bis-alkanes are obtained directly when primary diamines such as ethylenediamine, propylenediamine, butylenediamine and the like are reacted in the form of dihydrohalides with an oleinic compound and formaldehyde in accordance with the following equation:

where n is greater than 1.

In the following discussion as in the drawings the hydrohalide of the amine is numbered with Roman numerals and the corresponding free amine by the same Roman numeral with the addition of the letter a. Thus, Compound III (HX) (HX) (l) -OCHzN-(CHDn-NCHZQ- -C H2 CH2 C Rill is the N-methylol-tetrahydro-LS-oxazine hy drohalide and IIIa is the free amine.

In general, the present method provides for reacting an olefinic compound having a composition corresponding to the formula Rl \Rlll wherein R, R', R and R" represent the substituents enumerated hereinbefore, with form--` aldehyde; i. e., either an aqueous solution thereof or in the reversible polymeric form and a hydro- Cnalide of ammonia, hydroxylamine, a primary amine, or a primary diamine.

It is to be noted that gamma-hydrox'yalkyl-'l formaldim'ines are only formed when an am-v monium halide is used. When a primary amine halide is used N, N '-bis-methanes corresponding to the formula where Y is alkyl having not more than 18 car# In addition the N-substituted mono or di-substituted `ltetrahydroeL3='-.oxazinef isiormed.

-.n :fthe other fhand when' hydroxylaminev is usedaonlyrthe N-hydroxylwmono orpdiesubstituted tetrahydrosls-.oxa'zine is obtained.` 1'

Therefore, ltlierst step ofthe. reaction is illustratedfby the tollowingequations:

(o wsenismdrcgen 7 10 (3)- Whei ishydroxyl It will be appreciated by those skilled in the art, that a detailed description of the treatment of all of the reactants represented by the general formula giyenfhereinbefore is beyond the scope of -tl(1is disclosure. However, it is believed that the'ffollowing illustrative lexamples taken :in conjunction with the general discussion given herein will suffice for a complete understanding of the scope of the present invention.

. EXAM-PLEI, y*

.One mole vof' `hydroxylamine'Jhydroolfrloride .(510

' parts by weight) and 8'5v parts by weight of an aqueous f solution containing 36 per .cent form.- aldehyde (1 `mole) lwere mixed. vThe :temperature rose andlupon fallingtoabout 30:o C. about I52 parts by weight (0.5 mole) ofstyrene'were added. In the absence of external heat, the temperature ofthe resulting mixture .slowly rose to 40 C., and was held atlo i 3- C. byexternal cooling. 'The reaction mixture was agitated and held at'40 i 3 C. vfor two hours untily thetemperature fell to about`30 C. The reaction mixture was cooled further, unreacted hydroxylamine filtered off and theltrate `'diluted -With 100 parts by Weight .of Water. vI'l-iet'solution thus obtained .was extracted withy diethyl ether andthe ether remoyled lon a steam bath. Only labout one part lay-Weight of unreacted styrene'was recovered from theether extract.'v The :aqueous solution a'fterfextraetion with thefether Wascausticized with about 'one mole of sodium hydroxide in :the form of a 20 56.7 per cent''aqueouss'olution` The causticized aqueous! solution Waskthenextracted vWith diethyl ether andthe 'ether solutionevaporated to yield about 72 parts by weight of a light-yellow,=vis .cous amine as a residue. The-amine was found to havea nitrogen content of 6.58 lper cent.

EXAMPLE. 2

YAbout; 170 parts by weight of ian aqueous 36 per .errt solution oi." formaldehyde' (about 2.0V moles) and about 54 parts by weight of ammon-ium chloride (about 1 mole) were added to about 52 parts by weight-ofjstyrene (about 0.5 mole). The xreaction mixture s o-formed W35 agitated andwarmed tov about C., held' at about 80 C. for thirty minutes, cooled and about 30"parts by Weight of unreacted styrene and probably reaction products of styrene and excess formaldehyde rgtfllfioyeiiI 'I he aqueous layer was treated With about .one mole of sodium hydroxide as a 20 per cent aolueousl solutonand extracted with diethyl ether. The ether"l extract was `evaporated to yield about 44 rparts by` Weightofa 1igilt-yellowI viscous oil Which crystallized upon standing. The crude amine-had a nitrogen content' of7.80%`.

. esample' of .the ASemi-fifystalline amine was dissolved in alcohol.- A white crystalline mate- 11 12 rial separated upon cooling. After three recrys- 80 C. at which temperature the reaction became tallizations from aqueous alcohol the product a clear, homogeneous solution. The temperature melted at 126.5127.5 C. and analyzed as folbegan to fall and was allowed to 4drop to room lows: Carbon- 74.11 per cent; hydrogen- 7.75 1 temperature (20 C.). -The solution was causper cent; nitrogen-8.31 per cent; molecular 5 ticized with aqueous 20% sodium hydroxide soweight (boiling point method) 376. lution and a very viscous colorless liquid sepa- These values check very well for the calculated rated. The mixture was extracted three times values for a Compound V type material where R with diethy1 ether and the extract dried over anis CSI-Is and R', R" and R" are hydrogens. hydrous calcium sulfate. After drying and re- OH CH 1 0 moving the solvent, a very viscous liquid re- "\5 OCH,N CH N CH,O 5 mained. Analysis of this liquid showed that it /C- C\ contained 7.79 per cent nitrogen, the calculated H H nitrogen value for a compound of the type of IIa; i. e., H H

-C CH2 Cna- C- H H 05H5 -0 CHzNH H -CHz is 7.917 o H N \C v Percent Percent Percent H/ Calculated for CnHnNgOn 74. Found 74. y 5

CalculatedMOleCUlafWeight338iflm 1375- 25 In a. manner similar to'that described in Ex- EXAMPLE 3 ample 2 hereinbefore about 100 parts by weight of alpha-pinene (about 0.73 mole) were reacted Thirty parts by weight of paraformaldehyde with about 170 parts by weight of a 36 per cent (about 1 mole of CHzO) about 54 parts by weight aqueous solution of formaldehyde (about 2 of ammonium chloride (about 1 mole), 4and about 30 moles) and about 108 parts by weight of ammo- 105 parts by weight of glacial acetic acid and nium chloride (about 2 moles). Upon cooling about 10 parts by weight of water were added to e about 70 parts by weight of unreacted material about 56 parts of diisobutylene (about 0.5 mole) .Y was recovered and about 47 parts by weight of an The reaction mixture formed as described herefx; oily, viscous, light-red amine having a nitrogen inbefore was warmed to about 65 C. at whichv 35 content of 6.76 per cent was recovered. temperature a noticeable reaction started. The EXAMPLE 6 source of external heat was removed but the tem.-

perature rose to about 74 C. before beginningto About 104 Darts by Weight Of styrene (ahut fall. Thereafter the temperature was main- 1 mole). about 335 Darts by Weight 0f an aqueous tained at about 70 to about 73 C. for about one 40 36 per cent formaldehyde solution (about 4 hour. The reaction mixture was cooled and moles) and about 108 parts by weight of amparts by weight of unreacted octylenes recovered. mOnium Chloride (about 2 moles) Were mixed, The residue was neutralized with three moles of agitated vigOrOuSlY and heated t0 about 80 C. sodium hydroxide as a per cent aqueous som.. The temperature of the reaction mixture was tion and extracted with diethyl ether. The ether maintained at about 75 to about 80 C. for about,

extract was evaporated to obtain about 41 parts 2 hours. The reaction mixture was cooled and by weight of alight-red, viscous amine. Analysis extracted with diethyl ether whereby about 45 of this product indicated that the nitrogen conparts by weight of unreacted styrene were retent thereof is 6.34 per cent. covered. y A

This product was contaminated with by-prod- The pI-I of the extracted aqueous reaction mixuct m-dioxane and contained as its principal ture was raised to about 4 by the addition of 20 constituent a bis-methane corresponding to the per cent aqueous sodium hydroxide solution and formula: the resulting solution steam distilled (about 105 y CH; CH: CH3 \c-' -c/ CH,

d EXAMPLE 4 C.) for about 2.5 hours. During this distillation about 250 parts by weight of Water was added.

About :mty-nine parts by weight of alpha'- 'I'he distillate was extracted with diethyl ether methyl styrene and the extract dried. After removing the sol- CH vent from the dried extract about 9 parts by Cms-0:01a, weight of oil remained. An additional 4 parts by (about 0 5 mme)y about 167 parts by Weight, of weight of oil were recovered by extracting the rean aqueous 36% formaldehyde solution (about 2 acido!! mixture and treating the extract as de' moles CHzO) and about 54 parts by weight of 70 Scrlbed helelnbeforeammonium chloride (about 1 mole) were mixed, A SemCaIbaZOne Was prepared from this DlOdagitated vigorously and heated to about C. uct. The melting point thereof after reorystal- The external source of heat was removed and the lization from per cent ethanol was Z22-223 C.

temperature of the mixture rapidly rose to about Upon analysis the composition -of the semicar 83 C. The reaction mixture was cooled to about 76 bazone was found to be: Carbon-58.17 per cent;

hydrogen-.566 per cent; and a nitrogen-:25:68 per cent. These valuesare to be comparediyvith the calculated'V valuesicr CS HQNSG; of carbon-fI 513.89 iper cent;- hydroeen5-52 per cent; and'nitragen-25.77' per cent. The observed' valuesl aereemith thezcalculatedvalues forthe vsemicarbazone of benzaldehyde. Upon mixing the prepared lSemicarbazone .with anauthentic, sample-or Athe; semicarbazone; of benzaldchydel and determining y.the melting point; ofthe mixture no depression. of the :melting`v point was' observed.

The reaction mixture was causticizedjyvithq percent aqueous sodumhydroxide solution `and extracted with. diethyl .ether2 The .extract was dried :over anhydrous calciumsulfate `(other dryinezagents or this` type can be used). and; the.

Solventremoved. Seventyftwo, parts by'weightof product were obtained. Sixty-ifzourparts-by Weight' of 4theproduct were: distil1ed ,with the results as indicated by the `following log o f the distillation.y 1

Table I l Pot Vapor Pressure, i Parts Fraction No. Temp., emp., mm. m `by C. C. Hg Weight A methiodide Was prepared from fraction #3 Whichafter recrystallization from absolute ethano1 melted at -177-177.5 C. This methiodide was analyzed;` the observed values are compared with the calculated values of Cial-ImNO` hereinafter:

Carbon Hydrogen Nitrogen Calculated for CHHUINQ; 45.15 5. si' 4. 3 9 Observed 45.76 "5;18 4.38

It follows that the structure of the methiodide corresponds to the followingV formula:

Removal of the solvent left ..2 2 parts by Weight of a light-yellow oil possessing the strong, penetrating odor of an amine.

This material YWhen analyzed vcontained 11.5

per cent otnitrogen.v It reacted with phenyl iso- A thocyanate. togvea phenylhiourea .and formed a crystalline picrate ,when treated With'pic'ric.

14 acid.. After three r ecrystallizations;fromvethanole the picrate melted at 160.-.16 1 C. The crystals-- line picrate was analyzedfthe. observed values are compared with the calculated valueSwhere inafter. l

About 50 parts by Weight of amine )obtained as described in prior example from styrene, lform-` aldehyde and ammonium chloride (Examplelb).l were dissolved in about 1'70 parts by weight, of. benzene. About 108 parts by Weight of 95 per cent acetic anhydride? were added to thesolution of formaldimine. After the initial heat of reaction had subsided, the reaction mixture was heated on a steam bath (9095 C.) for about 1 hour. Polymeric formaldehyde condensed l upon the cooler Walls of the reflux condenser during this period. The benzene Was removed by .evaporation and the residue warmed toabout: 15G-160 C. at a pressure of 15 mm. of mercury to remove all of the unreacted acetic anhydride and free acetic acid.` It would be expectedthat,suchtreatment would cause pyrolysis of an: aralkylacetate that formed with .the splitting oi of acetic acid.,

The pressure was then reducedto 0.9 mm.-of mer.- cury and the distillation continued. The .disftillation was discontinued when there were about 24 parts by weight vof pot residue. Upon standingat room/temperature (about 20"l C.) for about lhours both the distillate and the residuel @Tystallized. After twg vrecrystallizations from n heptanethe crystals fromthe distillate melted at 839-835 C. Thecrystalline product fromgthe:

distillate was analyzed; the, values s o -.obtained are. compared` with the, calculated values iorV C12H15NO2 hereinafter Carbon Hydrogen Nitrogen Calculated for CmHNOz- 70. 24 7. 32 6. 83 bserved 70. 38 7. 55 6;-74-

Thus, it would appear that the crystals are those of a compound having a .composition core., responding to the formula \C o@ -OoHzNoocH H -t'iHi \C y H/- .l derived from a compound` having thefstructu-re o' ,-ooHQNH n\ -cIH'z \.o- H/ About 20 parts by weight of the crystals obtained as aforedescribed f romthe distillatewere dissolved in about y parts-byweght of zoper cent aqueousy sulfuric acid and .warmed .on a steam bath (909.1-.959 5C.)` for lfour hours.v 'v

. .ISF actionamixturewas cooled dhd20 parte by-weight.

l of sodium hydroxide added slowly. The causticized reaction mixture Was then extracted with diethyl ether. Evaporation of the ether left a pale-yellow amine which formed `a crystalline phenylthiourea when treated with phenyl isothiocyanate. After three recrystallizations from absolute ethanol the phenylthiourea melted at 127.5-128.5 C. This phenylthiourea was analyzed; the results are compared with the calculated values for CmHisNzOS hereinafter.

Carbon Hydrogen Nitrogen Calculated for C11H1N20S 68. 45 6. 04 9. 40

Observed 68. 29 6. 25 l0. 01

This corresponds to the formula A methiodide of this amine was prepared which after two recrystallizations from ethanol melted at 17'6177 C. A mixed melting point with the methiodide of Example 6 gave no depression of the melting point.

EXAMPLE 9 Example 2v was repeated using about 5 moles of styrene, about 20 moles of formaldehyde (in aqueous solution) and about 10 moles of ammonium chloride. The reaction mixture was heated for three hours. After cooling, the reaction mixture was extracted with diethyl ether and about 1 mole of unreacted styrene recovered. The extracted reaction mixture failed to crystallize even after seeding. A portion of the reaction mixture Was distilled as indicated in the Fraction #2 formed a phenylthiourea which after recrystallization from Formula #30 denatured alcohol, melted at 124.5125.5 C. A mixed melting point of this phenylthiourea and that of EX- ample 8 showing no depression.

Fraction #2 also formed a methiodide which, after recrystallization from absolute ethanol, melted at 175.5176.5 C. This methiodide when mixed with the methiodide obtained in Example 6 showed no depression of the melting point.

EXAMPLE 10 About 300 parts by weight of paraformaldehyde (about 10 moles of CI-IzO), about 268 parts by weight of ammonium chloride (about 5 moles) and about 90 parts of water (about 5 moles) as a depolymerizer of the reversible polymer of formaldehyde were mixed and placed in a reactor equipped with a stirrer. About 280 parts by Weight of liquid isobutylene were charged to the reactor by displacement With a measured volume of ethylene glycol.

The reactor was heated slowly t0 about 165 F. and the source of external heat removed. At this time the pressure within the reactor reached about p. s. i. (gauge) and then began to drop rapidly although the temperature of the reaction mixture continued to rise to a maximum o1' about 225 F.

After the temperature of the reaction mixture had fallen to about F. the stirrer was stopped and the unit allowed to cool slowly. After about 16 hours, no pressure was recorded on the gauge; an indication of substantially complete reaction' of the isobutylene.

The reaction mixture was extracted with diethyl ether and the extract dried over anhydrous calcium sulfate. Removal of the solvent yielded 51 parts by weight of a pale-yellow liquid. About 40 parts by weight of this liquid were distilled in the manner and with the results indicated by the following log:

Pressure,

Fraction No. mm. Hg

Pot Residue o. u i'. 4445 Dark brown liquid Fraction #7 was analyzed with the results indicated below and compared with the calculated carbon and hydrogen content of CsHizOu Carbon Hydrogen Calculated for CqHuOq 62.07 10. 34 Observed 57. 55 9. 90

Subsequently, it was established that this material was contaminated with about 7 per cent of water and was an impure sample of tlA-dimethyL- 1,3-dioxane,

the soivent. About 316 parts by weight of this' asia-rw Vapor Pressure, Parts by zo Fractlon No 2 Tg5-1&1," nimo-Hg Weight n 5';-

45 98 9 48 98 22 1. 4080`v 66 32 10 l 1;-4392=y 67 32 10 1.4480-j 69 32 17- 1.4506l 61 8.5l 12- -1-.4544' 71 8. 0- 11 1:4586` 67 0.1- 9- 1-.46301 .c A 72 0.1-- 27v 1.4654-15 75 0.5- 6- 1=-4650.1 89l 0.8-A 13- 1.54714L 92 1.1 12- --1:4760 80 1.5 4 1.4785

lisi- F'racti'ons s; 5; izadi's' @use formes-minimiser: although-in the instarices-dfjfretis, sarlat the" formationisslower arid-the amount-of' 'artista une derivative from" the amine-islas; I the'presehceofWaterin virliic ith are soluble. 1"'firieltingv p'firit datering l a-Inixtur'e o'fthenietliioids"fromir ,tio/iis 8 and 15 gavens'gicantdepresso y tabiishing the 'identity or theinethldi" i EX@ Mpj---lll.

About V13411parts bly Weight of a 3.6% aqueous fsolu-tionfof'forniaidliyde and about 428fparts by cous liq-uid--Whichforicooling, set upto tacky,v semi-solid mass. During the disti-Ilationof'frjc# tions #l through #5, the receiver was immersed iria Dry Ice-acetone bath. Signs of decomposisealed and the mixture" hjeat'e'dsloitly'toa''riiaxi-` mum .temperature olf-'1559 F. at-Which-temperaei ture the pressure Wasj'103` p. 'il' (aii'g'el.' The'-E pressure fell o'if rapidly laneta-fixercooling-to145g tioriwer'eapparent at a pot temperature of 145 C. u F1' had fallen lto 35 pus'. i; (gauge) raction? Nitrogen analyses and molecular Weight determinations`vv of several fractions orti-1edistillatewere made :Withthe results .given in Table-Ila Tble'II` Obfserred: f Observed Fraction No. -Percent` lvl'olecular Nitrogen Weight It is apparent that fractions 3 arid 5 are contaminated with Water which can-be separated by adding potassium carbonateto the lower boiling fractions, separating the organic layer, and redistilling to obtain theLpure--anhydrous amine.

A crystalline metliidid was formed with the material of4 fraction #8 in the usual mannerby IIe-wher@ @delai-#GHS- ether.

calcium sulfate, the solvent-removed-and-57 The procedure of Example 11 was follwedex- :cept that the maximum reaction- A temperature attained was 144 F. lix'tractionl of the reaction mixture i yielded a-bit" Serpa/its byweightl of product `and extractiony offtherainate; ive., caustici'd" extracted reaction mixture, yielded` l 703 parts AhyfWeight,of amine.

- About i 10" per cent of the extracted -causticized reaction mixt'ure Wa`s`=-treatd with a'naii'int of potassium carbonate in excess of sthat required-tof saturate the solution' and extracted 'with holieth'yl After. drying-2 fand rernovingthe solvent 7 parts bylw'ei'ghtlofamin iwere obtained." 'lhl'sfi1 the yield* ofamine-can be increased-about-10-per cent by this procedure.

lIt is to loe-noted vthat thell'amines are-solublegin all proportions' irrwateran'd 'therefore aredi'i cult toV Aextract "from "aqueous V'slutio'sjf' ExMPLEis EXAMPLE 1i-'- yielded 59 parts by weight of product and extraction of the causticized reaction mixture yielded '713 parts by weight of amine. A sample of this amine was dried under high Vacuum over a drying agent and analyzed. The nitrogen content of the dried sample was 10.35 per cent.

Theamine product from this run was a clear, pale-orange liquid which does not change appearance on storage. The yield was comparable to the other similar runs but the product appears to be superior. Therefore, the time, temperature and pressure data are presented in the following log:

(It is to be noted that the reactor was warm (100-105 F.) when the reactants were charged. Therefore, no external heat was required to initiate the reaction.)

The products obtained by extracting the acidic reaction mixtures of Examples 11, 12, 13 and 14 were combined and dried over anhydrous potassium carbonate. The drying agent was removed and 198 parts by weight of product were distilled as follows:

Vapor Pressure, Parts by Fraction No. Tgnp., mm' of Hg nu Weight 35 atmos. 74 atmos. 1. 3762 7 77 atmos. l. 3799 6 80 atmos. l. 3829 4 85 atmos. 1. 3881 13 90 atmos. 1. 3930 13 95 atmos. l. 4006 12 100 atmos. 1. 4080 8 105 atmos. 1. 4133 5 115 atmos. l. 4180 10 125 atmos. 1. 4215 12 124 atmos. 1. 4224 26 124 atmos. 1. 4208 34 108 l. 0 1. 4362 17 14 132 1.0 1 4525 5 Residue 6 Fractions 6 through 11 were cloudy, containing some fluify, white solid, probably polymeric formaldehyde.v vThis same material coated the inside of the condenser tube of the still.

All of the distillate was combined and dissolved in about 180 parts by weight of diethylA ether and the solution washed with per cent aqueous sodium bisulte solution and thereafter With water. The washed ether solution was dried for about 6 hours over anhydrous calcium sulfate and then over anhydrous potassium carbonate for about 10 days. After removal of the desiccant and the solvent 98 parts by weight were fractionated through a column 12. 111.011.655 height.'

packed with glass helices.

The log of the distil-` lation follows:

Vapor P ressure, Parts by Fraction No. Tlrip., mm of Hg m20 Weight atmos. atmos. ether 23 atmos. 1. 3773 4 atmos. 1.3830 3 atmos. l. 4081 7 atmos. 1. 4210 5. 5 atmos. 1.4216 8 atmos. 1.4219 10 atmos. 1. 4219 l1 atmos. l. 4213 6 49-11 1. 4211 3. 5 l1 l l. 4218 3 Fraction #7 was analyzed; the observed values are compared for the calculated Values for CGI-11202 as follows:

Hydro- Carbon gen Calculated fOl' CgHuOg 62. U7 10. 34 Observed 62. 22 l0. 52

The calculated values are those for a compound having the structure dimethyl-1,3-dioxane EXAMPLEr 15 EXAMPLE 16 heated to about 70 C. The source of external heat was removed and the temperature of the reaction mixture rose to about 83 C. The temperature of the reaction mixture was maintained at about C. for about 2 hours. After cooling, the mixture was extracted with diethyl ether to remove unreacted styrene, m-dioxanes, acetic acid, etc., and then causticized. The causticized reaction mixture wasthen extracted with diethyl ether. Removalof the solvent yielded 12.4` parts. byfWeig'ht-of-amine Whichwas distilled asfollovvs:n

but did form a methiodide -and'fpicrate bygstandard procedures. After recrystallizing from 95 per cent ethanol, the picrate melted at 1579-1589.. C.

A..mixed .melting point with the picrate. 0111720 tained.,from styrene, ammonium chloride ,and formaldehyde-Which had been heated at reflux temperature for about tWenty-fourhours showed.;

After. xJolingand4 standing.. the reactionmixe. tureseparatedv intothree layers; I About ,Zldmolesd of.unreacted.styrenetdp..layer): .were .separated The middle layer appeared to. be an aqueous soluticzrzwhiletithe lcottomlayersmas antony-material'relatively insoluble :in vWater; The middle and bottom la'yers werev iextr'acte'd as one liquid with diethylwether; :AbdutgZBjfl-'parts 1 by 'weighti otfliquid uwere @recovered iroxnauthe. .extracuby 1f eyaporationof they `solvent: 'material was.;

- a mixturefofeunreactedrstyrenee m..dioxanes .and

other oxyeenated materials-'formed i by 'side' Are-` :l actions. .The aqueous-.middle .layer .and thenoi-lyf. bottom "layenwere-.then ltreatedseparately --w-i-th Y about 10 molesy ofysodiumfacetate and extracted vent4 l ZO-i'fparts 'fby "Weight of E"extract Werewob tained-"from -f the-aqueous Iayerfand i iabcutt188 'fparts by-ffweightf ofmaterial from" the extract of f `tl'iefcily bottomdayer: 'These'extrac-tswere comw bined 'and distillew under a -va-cuumfas y'fol'l'oyvst Vapor no..depression.. An analysis of this latter amine;y Fraction No Tempi v P;gssum, um Paris by K pcratedscomparedwith the calculatedvaluef `o:`' mm`fHg Weght for. :1 -compound corresponding to theempirical` ormllleCivI-IiaNfiOs asfollows: (111,1 0 @4l 4g as.' f Percent Percent '30 l. Percent i 2 Hydro- Nitro- Y 0,6 A. A13 5 Carbon gen gen l 0.8 1o;ll`

292 2.0 .23.. 5. Calcu1atedf0rC11H1sN40s 50. 25 4.43 1379. RSdue.- 35"? Ob'servedr. 49. 89 4. 59 13.93

Thus, -it fiszraparent' that the amine obtainedas described hereinbefore has -a composition, cor--l responding to theV vformula 'Aftertrecrystallization fromY absolute-ethanol,- the-methiodide obtained from fraction, #2 .melted at -178178.5C`.j Afmixed melting point 'deter-- mination of 'this4 compound andthe .methiodiden of-i-the amineobtained in Example Gishowedno'z depression of; themelting point.

'Fraction-'#5 -did .-not forma vmethiodide' but" did-form-a--picrate Yand a phenylthiourea when 50 reversible epolymer...ci. iormaldehydej" ''hewre-65 y fA'ft'er Fraction #7 was removed, the decomposif. t1on-became1appa1tent andwater collected in'V the.

aetionetmixture was agitated. vigorouslyy and warmed-.to :552.1 C.: The source of.externall-heatvwas removed and the temperature of the-mixture-- rosextof" C;` Thereaiterthe: reaction mixture turefwasfallowed r:to :fall and .Was Y controlledf-.atx aboutr -801eto ,185, C.. The reaction'. .mixture CAVwas heldfinzzthisflatter.'temperature. range for aboutY 6 hours.

l Aceticfecid{ftemperaturevandpressure riotconstant.A

Weight-offV thi-srfractionmwasu'252: f The residue;v was analyzed and foundtd'contain 4.93"per cent nitrogenandtohavea lmolecular dWeight' of`-'521..

lThe organi@ material" (bottom layer) f and `the:

aqueousf'middlelayer-were combinedandtreatedi causticized mixture was then extracted With'di* Fraction No. mm.,0f Hg Geld trapr,

`Upon analysis'fraction #ify uvas foundv to. .conn tain 74.70ipere'centnarbon;-8331 percent hydro fgen'sand zzlfflperf 'cent nitrogen. The aqueous layer from; the last extractionwasqf treated withzlO moles of :sodium hydrbXideandafter coolingr. waslextracte'df-yvith zdiethyletherr:`

After removal ofthe solvent'from..the.-extractu;

23 212 parts by weight of amine were obtained. This amine was distilled as follows:

Vapor lressure Tgrl?" mm. of Hyg Parts by Fraction No. D Weight Fraction #2 was analyzed and found to contain 8.95 per cent nitrogen. When treated with phenylisothiocyanate Fraction #2 formed a phenylthiourea in the usual manner. After recrystallization from 95 vper cent ethanol the phenylthiourea melted at 92-92.5 C. Upon analysis it wasl found that the phenylthiourea derivative of fraction #2 contained 70.77 per cent carbon, 6.66 per cent hydrogen and 10.60 per cent nitrogen.

` EXAMPLE' 18 .About 15 moles offormaldehyde (as an aqueous `35 per cent formaldehyde solution) and about 7.5 moles of ammonium chloride were' added to about 5.25 moles of alpha-methyl styrene. The mixture was agitated vigorously and heated to 66 C. The source of external heat was removed but the reaction temperature continued to rise. When the temperature of the reaction mixture reached 79 C. external cooling was resorted to but the temperature continued to rise until a temperature of 86 C. was reached after which the temperature began to fall. .After the temperature of the reaction mixture had fallen to 80 C. external cooling was discontinued and the reaction temperature allowed to fall slowly to room temperature (20-25 C.).

The reaction mixture was extracted three times with diethyl ether. Removal of the solvent from this extract left about 38 parts byweight of liquid which consisted primarily of the methylphenyl-1,3-dioxane.

The raffinate or extracted reaction mixture was causticized with 28 per cent aqueous ammonium hydroxide and extracted with diethyl ether. Removal of the solvent yielded 819 parts by weight of liquid product. About 719 parts by weight of this product were distilled under reduced pressure. The data of this distillation is tabulated as follows:

l Ethel'.

After standing about six weeks the distillate became very viscous. At that time the products were analyzed with the following results:

Percent Molecular Fraction No' Nitrogen Weight The raiinate from the second extraction was causticized with 200 parts by weight of sodium hydroxide and extracted with diethyl ether. Removal of the solvent yielded an additional 82 parts by Weight of product.

EXAMPLE 19 About 11 moles of formaldehyde (as a 36 per cent aqueous solution) and about 5.5 moles of ammonium chloride were added to about 5 moles of alpha-methylstyrene. The reaction mixture was stirred vigorously and warmed to 65 C. The source of external heat was removed and the temperature of the reaction mixture allowed to rise to about C. and held at that temperature for about 1 hour. Thereafter, due to failure of the cooling system, the temperature rose to about 97 C. The mixture was 'cooled to about 80 C. and maintained at that temperature for about 3 hours and then allowed to cool to ambient temperature (20-25 C.).

The reaction mixture was treated with about 6 moles of sodium hydroxide and extracted with diethyl ether'. hydrous calcium sulfate and the solvent removed. About 754 parts by weight of product were obtained. The product was distilled under :reduced pressure as indicated by the following log of the distillation:

1A black solid. Analysis: Fraction #l-7.01 percent nitrogen. Residue-5.02 percent nitrogen; molecular Weight, 367.

It is to be noted that since the reaction mixture was not extracted before causticizing, the product contains dioxanes and consequently the nitrogen content is low.

Fraction #6 reacted with phenylisothiocyanate but the phenylthiourea could not be crystallized. However, a crystalline methiodide was prepared from fraction #6 in the usual manner With methyl iodide. The methiodide contained 49.26 per cent carbon, 5.77 per cent hydrogen and 4.76 per cent nitrogen.

The crytals from fraction #10 were digested with boiling ether and then had a melting point of 159-160.5 C. After recrystallization fromV Water the product melted at 159.5-161 C. Upon analysis the recrystallized product was found to contain 73.12 per cent carbon, 8.54 per cent hydrogen and 7.66 per cent nitrogen.

The crystals obtained by recrystallization from The extract was dried over an- 12E',l`v 'water were lrecrys'tallized C frln beiizee and -Washed' with petroleum-ether'. @After thistreiatmentj the2 melting .Lpoint Was A1593504l'GOlVfC. After.' drying infivacuur'n thef crystals"y Weieanalyzedandifound.` to: cont 74LB7f-"lperfeet 4earbon, 1 8.'59fper' centi hydrogen fand- 8.28 515er cent nitrogen.

yAbout 2 Imoles f ofi formaldehydetasaf 3 Signer icent aqueous solution) 'andabout' \1"m'ole"o'i thylamine `hydrochlorideiwere'adiiled toabou =`l1 mole of alpha-methylstyrene. The reactie'r'rnixture Was agitated 'and'fheatedlto about 70-about .75 C. for about-2 hours` After cooling toaxnbient temperatures (20V-25 C.) Qthy'e reaction f mixture Was` 'extracted `with `diethyl ther. "'Ilhe extract 'Was' 'dried' over anhydrous calci-uni-Tsulffate;l` the 'solvent removed and about 148 parts by weightof organic material recovered.

The extracted reactioninixture (rainate) was treated with about 1.5'moles of sodium hydroxide (as a 30 per cent aqueoussolution) and the causticized reaction mixture or ranate. extracted fwithtdiethylether. The extractivas-dried and thesolvent removed t''yield about 1'55 'parte by Weightof amine.

` A picrate was prepared"`rom"this'arninejby standard procedures' 'thenieltin'g Doi'nt 'of which after' recrystallization from absolute? thanolivas V240-`-2'41""C. (corr.). .The pic'rate' wasV analyzed. 'The' analyticalresults are comparied'-witli`-the calculated values for ClaHzoNiO in the`"'fllovi`rg tabulation:

rI'hese analyses establish that'thea'mi'ne from which this picrate was-prepared had a composition corresponding to the following formula:

The remainderv @mms-.amine (about roefpartsby Weight) was distilled as -indicated'in the following log: I

Fractions #2 through #5` are primarily fffan amine Vsuch as that fro'rn'whicli thepierate'was prepared. Fraction #became'viscous' and began lto crystallize. f Fractions #7 and #8-Were crystalline. After recrystallization I`fimbenzene C. Analyses of these crystals are compared with itheifcaloilatedfiialues for CsHuNzOz 'in the "following tabulation:

CarbonV Hydrogen Nitro-gen `Percent u Percent n' Percent .i9 7. 57 1 S 98 Observed; I

-f'lhese'fvaluea indicate that '-thev aminefinfquetion erection #s formed.: a .-meuhiodide when treated Percent l 45.87 3162 32 Percent 6. 12

Percent y A l 4. 28

About 4 moles of `animotrium""chloride and about -efmoiee ofwionmaldehyde (as': a y3 6%A aqueou'soa "lllonviiiere plfaeed'fin'a pressurev resistant "con- :tainervandf'aboutlffl-moles of liquid -1"b"u'tene charged fto 5the f container. The "containerV was -sealedifand heated feto. `a maximum temperature of; about-l=65i 'Whilei-agitating"the-contents.

The-reaction mixtureWas` allowed "to 'cool =to '110 F.,-ithe`"container vented `andthe reaction mixture vcooled-'tol ambientftemperatre (20'251C.). IUndissolved an'nnoniumv chlori'c'le'y wasl 'removed and the residual reactionf mixturef extracted-'I'With' diy:ethyl "ether: f- Thefextracti AwasI dried and thesola verrviremovei.Aboutliparts by `weight :of liquid producen/ere' recovered.

.The 'rainatefwas'ftreated fwith excess`vl sodium hydroxide ',(abou'tD 3.75 moles) 'and allowed't'o cool -to` room-temperature (12W-2580.). l The@ caustcize'd'rafnat'e' W'a's extractedwith diethyl ether andiried.` .Upon'v'removal of the 'solvent' about parts by1-weight"of amine were f obtained.

`About 8.49uncles'Y of: formaldehy"de (as a" 36% aoueoi'Vsl-soliitinyi and about 411 moles 'of "ain- 'moniu'ih chloride 'were added to about3'00' parte` by weight of a mixture containing 38.6 per cendivinylbenzene, 1127 per cent'diethylbenzena 43.6 -per "c'ent ethylvinylbenzene and 6 per fcent high boi-ling material.l The reactionvmixture Lvlas 'agi- -ta'ted and-heated tofabout-a80 C. The temperaitureoffthe 1reaction --mixture was maintained 'at about 75to about 80C; for-lfl'iours.` -Thelreactionrfmlixturelywasrfcooled to 'i room' temperature and t1*eatedwzitlrabout?5y molesof sodium-hydroxide lasfaafilllper cent-aqueous:solution). After the additie'n of. the* caustic f solution -the jcolor.` `of thefre'a'etion f-mixt'uref changed from pale lorange :to darkffbrowril and 'asemi-resinousH ma'ss'sepa rated. A

#The f.mixture-was-:extracted withdiethyl :ether in-Which'onlwafportionof lthe resin'ous material dissolved. The ether solution was left in Contact with the resinous mass for about 16 hours and EXANIPLE 23 About 2.1 moles of ammonium chloride and about 2.3 moles of formaldehyde (as a per cent aqueous solution) were added to about 1 mole of 2ethyl-1-hexene. The mixture was agitated and heated to about 65 C. The reaction mixture was held at a temperature of about 65-69 C. for about 2 hours. The temperature of the reaction mixture Was then raised to about 74 C. (reflux temperature) and held at that temperature for about 2 hours.

The reaction mixture was cooled to room temperature and about 0.9 mole of olen recovered.

The aqueous portion of the reaction mixture was treated with about 2.5 moles of sodium hydroxide (as a per cent aqueous solution) and extra-cted with diethyl ether. After drying and removing solvent about 25 parts by weight of liquid product were obtained. This product had a nitrogen content of 9.66 per cent.

EXAMPLE 24 About 8 moles of formaldehyde (as a 36 per cent aqueous solution) and about 4 moles of ammonium chloride were added to about 2 moles of 2-methyl-1-pentene. The reaction mixture was agitated and warmed to about 53 C. The source of external heat was removed but the temperature of the reaction mixture rose at the rate of about 1 C. per minute to about 60.5 C. The temperature of the reaction mixture remained Substantially constant at 60.5 C. for about 15 minutes and then began to fall slowly. The reaction mixture was allowed to cool to room temperature and the organic layer (about 68 parts by weight) was separated. The remaining reaction mixture was extracted with diethyl ether and the extract dried over anhydrous calcium sulfate. Removal of the solvent from the extract yielded about parts by weight of liquid.

The extracted reaction mixture; i. e., rainate was causticized with about 8 moles of sodium hydroxide (as a 40 per cent aqueous solution) and extracted with diethyl ether. This extract was dried over anhydrous calcium sulfate. The solvent was evaporated and 237 grams of amine recovered, which had a nitrogen contentof 11.29 per cent.

EXAMPLE 25 About 8 moles of formaldehyde (as a 36 per lcent aqueous solution) and about 4 moles of ammonium chloride were added to about 2 moles of 2ethyl1butene. The reaction mixture was stirred and warmed to about C. The source of external heat was removed but the temperature of the reaction mixture continued to rise at the rate of about 1 C. per minute until the reaction temperature reached about 61 C. The temperature of the reaction mixture remain substantially constant at about 61 C. for about 10 minutes. Then the reaction mixture began to fall and the reaction mixture was allowed to cool slowly to ambient temperature. The organic layer (about 104 parts by weight) was separated from the aqueous layer of the reaction mixture and the latter extracted with diethyl ether. This extract was dried, the solvent removed and about 30 parts by weight of liquid product obtained.

The extracted aqueous layer of the reaction mixture; i. e., the raiiinate, was causticized with about 8 moles of sodium hydroxide (as a 40 per cent aqueous solution), cooled to room temperature and extracted with diethyl ether. The extract was dried, the solvent removed, and 184 parts by weight of amine obtained. Analysis of the amine indicated a nitrogen content of 9.50 per cent.

EXAMPLE 26 About 1 mole of ammonium chloride, about 2 moles of formaldehyde (as paraformaldehyde) and about 1 mole of water (as a depolymerizer of the-formaldehyde polymer) were added to about 1 mole of allyl alcohol,

The reaction mixture was agitated and heated to about 65 C. The heat of reaction raised the reaction temperature to about C. The temperature of the reaction mixture was held at about 80-85 C. (by external heat) for about 2 hours. `The reaction mixture was then cooled and about 198 parts by Weight of ethanol were added. About 0.3 mole of ammonium chloride was removed.

The reaction mixture was evaporated to dryness and the residue treated with about 1 mole of sodium hydroxide and about 60 parts by weight of water. About 25 parts by weight of water were added and the resultant mixture extracted with diethyl ether. After removing the solvent about 6 parts by weight of light-red amine were obtained. The nitrogen content of this product was 15.72 per cent.

EXAMPLE 27 About 0.5 mole of ethylenediamine dihydrochloride was added to a mixture of about 1 mole of styrene and about 2 moles of formaldehyde (as a 35 per cent aqueous solution). The mixture was heated to about 70 C. and the source of external heat removed. Thereafter, the temperature rose to about 76 C. Thereupon the reaction mixture was subjected to external cooling but the temperature rose to about 77 C. and then began to fall. The source of external cooling then was removed and the temperature continued to fall. When the temperature reached 65 C. heat was supplied to the reaction mixture and the temperature maintained at about 65- 70 C. for about thirty minutes. Thereafter, the reaction mixture was allowed to cool to ambient temperature (15-20 C.) and the reaction mixture extracted with diethyl ether. The extract was separated and dried.

The extracted reaction mixture was treated with about 1.1 moles of sodium hydroxide (as a 40 per cent aqueous solution) and cooled to ambient temperature. The caustcized reaction mixture was extracted with diethyl ether and the extract dried. The solvent was removed from the dried extract to yield a dark-red, viscous liquid which began to crystallize. After standing about four hours the crystalline product was separated. A portion of the crystalline product was recrystallized from per cent ethanol. The recrystallized product was analyzed and found to contain 75.17

per cent carbon; 8.16 percentzhydrogen and 8.10 per cent nitrogen. The'zmelting point of the recrystallized product Was 1409141-9 C. (corr.).

The calculated'values for carbon, hydrogen and nitrogen for ascompound having: a composition corresponding to CzzHzsNzOz are compared with the values observed for the recrystallized material in the following tabulation:

' Percent Nitrogen ` 'Percentv Hydro-g gen Percent Carbon 'onttntedifofesnsmot 7,95" Found 8. -8;-10

Therefore, it would appear that the white crystalline material has a composition expressed 'by the formula:

`Asrnall amount/'of ether-insoluble materialwvas recovered from thescausticized reaction material by ltration. I'Ihis materia] `WasWa-ter-Waslfled, dried and vfound to contain 8.99 per cent-nitrogen.

EXALPLET .28

About 1.2 moles of beta-pinene were added to afmixturel` of @about lzmoleaof'. ammoniunichloride and `about Zamoies*'ofcfformal'dehyde :fase: 3643er cent-u` aqueous==so1uti`on).. .Thesfreactioxrimixture was 'stirred andfduringfa period'cf about L10minutes theftemperaturelof lthe'reactiorrmixture .rose slowlyto about 682C. v.Thereaction:mixture'fvvas allowed to cool. slowlyl tov room temperature and extracted with.4 diethylf ether. The .extract kwas driedtand rabout-98 i partsfby weight-of -liquid'obf tained. @About- 87: lpar-.ts -by weight of. :this "liquid Were distilled. The log of this distillation s=pre sented-:in the .following-tabulation:

Fraction N o. L

About linole ofammonium chloride/aboutMZ inblesof 'formaldehyde asiafd p'er'c'en'ti aqueous sumti-@nr and aboutv tamales bf'watef were mixed and ailowed to co'ol to room temperature. .Whilst 'ths' mixturewvas stirred about Y1 v.mole .f' beta.- pinene was added -sl'ovvly" over a'perid' Aof'i Nril'iutes. The;` "temperature: jf. 'the "reaction mixture began to'riseslowly and,jabout' 30 minutesafter `all of thei betaepinene'had been a'dddjr'ea'chd about 40 C. The*temperaturepfthe .reaution mixture Was-held at )40 -"2"C.'by externac'ooling. "Aften about 20 minutes "the" temperature of the reaction mixture'began to""fa1l.""The reaction mix'- -ture' Was allowed tocool slowly 'to roorntemp'erature 'and extractedwithdiethyl ether; Thf'ex- 'tract was dried-over 'anhydrouscalcium" sulfate, the solvent removed andabout74paTtsby Weight of organic-materialbbtainedx" I v "The reffinate'was cooled Ito'about"10""C"2and aboutflf mole of sddiuinv 'hydroxide""("asrayn Dper centaqueous` solution) was addedslovly; cDuring the addition-of thecaustic"th'temperature"f the Inixturewas maintained-'atabuti1020 C "The causticized vraffinate" was extracted with *diethy'l ether,- fthey solvent freinoved" and about" `1'02p`aJrts by .Weight of La light-orange s'liquidobtained fAboutfQ'parts by'wei'ghtof vvthis iiquidf'wasisubrjected 'tor a rreduced pressure of about' umrns'dof niereury foritabo'ut l'30 Aminutes', *At'rfthis treat# ment about '73 parts by Weight of the material remained. This material -had aV` nitrogen content of 6.90 per cent. EXAMPLE "30 About i moles of formaldehyde (as a 35 per cent aqueous solution) and about 2 moles of ammonium chloride were mixed...andi:r about 1 mole of dipentene was added to the mixture. The resulting .reactiontmixturetfwasoheatedtlslowly t0 about 75 C. and the temperature held between about 75 and about 80C. foriabout 45 minutes. After cooiing to room 'temperature about onethird of the reactant vseparated-.as an oily layer. The aqueous layer was causticizett with about 5.5 moles of sodium-hydroxide (asa 40 per cent aqueous solution) and the causticized reaction mixture extracted with diethyi ether.l yThe extract was dried, the .solvent removed anda viscous, liquid amine obtained. "`The"viscus'liqi`1id Yamine had a nitrogen content of 10.91 per cent.

EXAMPLE 31 Onemole I:each of ian'iline 'hydrochloride and styrenewere mixed V#With/about 350 part's 2 by Weight of water and cooled to about 1-0C. The temperature fof the mixture was held between about 10 and about 20 c. throughout the addition ofJ about:2tmolestofformaldehyde-(as31136 per cent aqueous solution). (About 30 minutes were required for the addition.) An orange precipitate formed. Agitation of the reaction mixture was continued for about two hours andthe precipitate removed. 'Iheiiquidreacition mixture was causticiZed with sodiumhydroxide andt'asmall amount of White resinous material recovered. -After thorough eiutriation With waterandurying, this material was found to contain 8.01 per cent nitrogen.

The orange..soiidwasdriedand tarpontionfboiled for three hours in about 15 times its weight of distilled water and an insoluble-resin removed. After dryingy the resin was found to contain '1.05 per cent nitrogen and 3.04 per` cent chlorine.

The aqueous 'solution"obtained by extracting the orange solid-With boiling Water was treated with caustic and the gummy material which separated Was dissolved in uboiIing benzene. Evaporation of the benzene yieldsa light brown viscous oil havinganitrogencontentaof 10.94 percent.`l

It is believed that the foregoing detailed discussion of the preparation of various amines by the application of the general principles of the present invention makes it unnecessartr to provide any further detailed discussion of the preparation of other amines and formaldimines. It is believed sufficient to name the olenic compound and indicate the formula of the resulting product.

The olenic compounds can be reacted with formaldehyde, either as an aqueous solution or as a reversible polymer of formaldehyde in conjunction with a suitable depolymerizer, including water, and a hydrohalide of ammonia or a primary amine or diamine in the proportion of 1 mole of olenic compound to at least one mole of formaldehyde and at least one mole of hydrohalide of ammonia or primary amine or diamine.

In further illustration of the generic concept of the present invention but not with the intention of limiting the scope of the present invention, the following examples are provided:

Z-ethyl-Z-butene can be reacted with aqueous 37 per cent formaldehyde solution and ammonium bromide at temperatures of about to about 100 C., the reaction mixture treated as aforedescribed, and the following products obtained:

Trimethyl-m-dioxane as a by-product Similarly, 2,3-dimethyl-1-butene can be reacted with aqueous 35 per cent formaldehyde solution and ethylamine hydrohalide, the reaction mixture causticized and the following compounds recovered:

Bis- (methyl-isopropyl-N-ethyl-tetrahydro-l,-oxazino) methane 2,3-dimethyl-l-pentene likewise can be reacted with ammonium bromide, paraformaldehyde and a depolymerizer such as acetic acid at temperatures of about 40 C. to about 140 C. When the acidic reaction mixture is extracted with a solvent the m-dioxane is obtained. When the extracted reaction mixture is causticized and extracted in a manner similar to that described in detail hereinbefore, the methyl 1- methylpropyl) -tetrahydro-LS-oxazine is obtained. It is to be noted that when the reaction is carried out at reux temperatures, the N-methyl compound specically is obtained. Consequently, (with this exception) corresponding products are obtained When 3-methyl-3-hexene is reacted with aqueous 37 per cent formaldehyde and ammonium halide.

When 2-methyl-l-heptene, formaldehyde and propylamine hydrohalide are reacted at temperatures of about 40 to about 150 C. the principal product obtained by extraction of the causticized reaction mixture is pentyl, methyl-N-propyltetrahydro1,3oxazine When 2,3-dimethyl-1-hexene is reacted with formaldehyde and benzylamine hydrohalide at about 40 C. to about 150 C. in a manner similar to that described more fully hereinbefore, the reaction mixture causticized, and extracted with a solvent such as diethyl ether, the principal product is methyl-(2pentyl) -N -benzyl-tetrahydro- 1,3-oxazine.

In a similar manner, When 2,3,4-trimethyl-1- pentene is reacted withv paraformaldehyde, Water Diisopropyl-N-methylftetrahydro-l,3-xazne and VBisdiisopropyl A`tetrahydro-l,S-,oxazino)l `.methane When '2-methyl-2-undecene -is reacted 'with aqueous 36 per cent "formaldehyde solution and ammonium :halide -at :temperatures tof about 40 C. to about `156 C. the iollowingproducts can be obtained ('1) upon extraction of the acidic reaction niixture, dimethyl-octyl-m-dioxane, (2) upon extraction of thecaus'ticized raffinate from the acidic extraction, hydroxy-methyl-noctylormaldimine, dimethyl actyltetrahydro 1,3- oxazine and .bis-(dimethyl'octyltetrahydro-l,3- oxazino) -methane When f2-fmethy'l-"2-heptadecene, paraiormaldehyde, acetic acid and methylaminehydrhalide are reacted in a manner sixnilaritofthat-described hereinbef-ore, `,the v4principal product of the extraction df the causticized reaction mixture is dimethyl tetradecyl ,:Nmethyl-tetrahydro-1,3-

oxazine.

When .239,11--1ino1eic :acid is reactedl with :paraformaldehyde, :acetic acid :and L'methylamine :hydrohalide in the manner described hereinbefore the principal product obtained uponextraction of the causticized reaction mixture is an oxazino derivative of l-the Vlinoleic acid.

An analogous ,product is obtained by extraction of the causticized reaction "mixture obtained by reacting linolenic acid, paraformaldehyde, acetic acid and methylamine hydrohalide.

Results similar in every respect are obtained when aromatic compounds lhaving olefinic side chains are treated in the manner-.described hereinbefore. For example, 'l-phenyl-l-butene When reacted With an excess of formaldehyde in the form of a 37 per cent aqueous solution and arnmonium halide yields as `the principal products phenyl-ethyl-tetrahydro-1,3-oxazine and bis- `(phenyl-ethyl-tetrahydro-13-oxazinel-methane.

Under the conditions described `-'hereinbe'fore Zephenyl-fiemethyl-Z-hexene mWhen Lreact-ed vwith formaldehyde land Lsecondary lbutylamine fas'fithe lhydrohalide yields tas the principal' =product its methyl-:phenyl-'secondary butyl-Nebutyl-tetrahy'- dro-1,3-oxazine.

A f similar Ireaction ftakes place ,with .the cycloparafins :having .an Junsaturated iside chain. For example, 2-ecyclopropyl-l-propene lreacts with :aqueous 37 :per cent .formaldehyde .fso'lution and .methylamine zhydrohalide. to yield, upon lextraction of the causticized reaction'fmixtureucyclopropylemethyleinethyl -ztetrahydro-l ,3 -oxaz'ine Similarly the 'reaction between .l-,isopropenyl- 2-methyle3-cyclohexene .(o-ementhadiene), paraformaldehyde, .aa depolymerizer, and .butylamine hydrohali'de yields, vupon extraction :of ;the -zcausticized reaction mixture, .(2=;methyl3'cyclo hexenyl) methyl N.zbutyl -tetra'hydro 1,3- oxazine.

Another illustration of :the general :concept .is the reaction lbetween 1emethyl-A-isopropenyl-lcyclohexen'e :(.di-pentene, limonene) ,'.paraformaldehyde, a depolymerizer and aniline hydrochlo- 'ride 'which yields, :upon extraction of the l' caus- .ticized :reaction mixture, i.('4'-methyl-'3fcyclo hexenyl) methyl -=1\T I- phenyl--tetrahydro- ,11,3- oxazine.

Stilbene (1,2-diphenylethylene) reacts with aqueous 37 per cent formaldehyde solution and benzylamine hydrohalide to yield, upon caustici- Zation of :the reaction mixture and extraction thereof, diphenyl-N-benzyl--tetrahydro-'1g-oxazine.

4'Viny'lphenol 4'reacts with yaqueous 37 per cent formaldehyde and 4propy'lamine hydrochloride to yield, upon extraction 'of the'eausticized reaction mixture, l:(hydroxypl'xenyl) -N-propyl-'tetrahydro- `1,*3-oxaz'ine.

-vinylguaiacol reacts with 4aqueous 'B'Tper lcent 'formaldehyde 'solution and vamylainine hydrochloride to yield, `upon lextraction of the causticized reaction "mixture, ('l'hydroxy2' methoxypheny'l) -LN-amyl-tetrahydro-1,3-oxazine.

Vinylacrylic acid CH2="CH-TCH=`CHCOOH When reacted' Withaqueous v.38 percent-formaldehyde and ammonium halide yields, upon extraction of the causticized :reaction mixture, the alkaline salt of an oxazino derivative of vinyl acrylic acid.

In a similanmanner when reacted with paraformaldehyde, a depolymeriaer and an ammonium halide, for example the chloride, yields, upon extraction of the causticized reaction mixture, phenyl-(l-methoxyethyl) -tetrahydr0-i1',3oxazine and the correspending di-oxaZino-methane.

In a manner analogous to that described hereinbefore propenylguaiacol v4can lbe reacted with paraformaldehyde, a depolymerizer and methylamine hydrochloride to yield, upon extraction of the causticized reaction mixture, (l-hydroxy 2Inethoxyphenyl) -methyl-N methyl tetrahydro-1,3-oxazine.

The heterocyclic compounds having unsaturated side chains also can participate in this reaction. ."I-hus, :for aexample, y'vvhcn .Z-Vinylthiophene reacts with aqueous 37 per cent formaldehyde and ethylamine hydrochloride, extraction of the causticized reaction mixture yields (2'- thienyl) -N-e'thyl-etetrahydro-l,S-oxazine.

Similarly, '2-methyl-i-vinylthiophene` when reacted with aqueous 37 per cent formaldehyde and an amylamine hydrohalide yields, upon extraction "of the causticized reaction mixture (2'- 

11. BIS-(TETRAHYDRO-1,3-OXAZINO)-ALKANES HAVING THE STRUCTURAL FORMULA 